JP2008086185A - Polymer actuator element and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer actuator element that exhibits excellent elasticity and response speed in an open system at room temperature under atmospheric pressure, and to provide a method for manufacturing and driving the polymer actuator element. <P>SOLUTION: A polymer actuator element includes a conductive polymer and a driving electrolyte. The driving electrolyte is a solution containing a nonionic organic compound that is in a liquid state at room temperature under atmospheric pressure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer actuator element. The present invention also relates to a method of manufacturing a polymer actuator element and a driving method thereof.

  A conductive polymer typified by polypyrrole or the like not only has conductivity but also can incorporate ions as a dopant, and can be repeatedly doped and dedoped by applying a voltage. Therefore, the conductive polymer can exhibit electrolytic expansion and contraction, which is a phenomenon that expands or contracts due to electrochemical oxidation and reduction. This electrolytic expansion and contraction of the conductive polymer can be used as a drive for the polymer actuator element.

  An actuator using a conductive polymer can reduce the weight of the entire device incorporated because it is lightweight, and can be used not only as a small drive device such as a micromachine but also as a large drive device. Expected. In particular, application is expected for uses such as artificial muscles, robot arms, artificial hands and actuators. For example, a linear actuator using polypyrrole exhibits an expansion / contraction ratio of 15.1% at maximum per one oxidation-reduction cycle by electrolytic expansion / contraction, and can generate a force of 22 MPa at maximum (for example, see Non-Patent Document 1). .

  However, a polymer actuator element using a conductive polymer has a slow driving speed such as expansion and contraction when a trifluoromethanesulfonate ion, which is a general anion, is used as a dopant. The polymer film could expand and contract only in a direction parallel to the film surface with a small expansion rate per specific time. For this reason, the polymer actuator element using the conductive polymer until now could be used suitably for the use which may be sufficient even if drive speed is slow. On the other hand, when driving a polymer actuator element using the above-described conductive polymer, it is necessary to devise measures such as increasing the size of the polymer actuator element itself in order to achieve a predetermined length of driving within a certain period of time. Met.

  In particular, in the case of a bimorph type polymer actuator element having a composite film in which a porous support is placed in the center, a metal electrode layer, and a conductive polymer laminated in this order in a sandwich shape, the entire polymer actuator element is filled with an electrolyte solution. It is impregnated or the composite membrane is impregnated with an electrolyte solution. Until now, a liquid containing an electrolyte salt in a low boiling polar solvent such as water or acetonitrile has been used as the electrolyte solution. It was. The reason why only these polar solvents were used is that they have a high affinity with conductive polymers, and it is easy to disperse electrolyte salts uniformly by using a polar medium, and also inhibit the movement of charges and ions. It was because there was not.

  However, when the low-boiling polar solvent as described above is used, in the state where the polymer actuator element is taken out from the solution and the polymer actuator element is installed in the air (that is, the air-driven polymer actuator element), the electrolyte Since the low-boiling polar solvent as a medium evaporates with time, no charge or ion movement occurs over time. Thus, it was found that the above-mentioned polymer actuator element used as a low-boiling polar solvent electrolyte medium cannot maintain the initial driving (displacement amount) for several hours when exposed to air without coating. . In addition, a proposal using a solid electrolyte instead of the electrolytic solution has been made, but in such a case, only a very slow operation with a response frequency of about 1 Hz can be performed (see, for example, Non-Patent Document 2).

  The polymer actuator element is preferably capable of repetitive movement, and the coating of resin or the like may be deteriorated or damaged. Therefore, it is expected that the polymer actuator element can withstand continuous driving for several hours or more in air without coating. It's getting on. However, until now, no polymer actuator element using a conductive polymer has been found that has continuous driving in air and can be responsively driven even at high frequencies.

Genji, 4 others, “High Stretchable and Powerful Polypyrrole Linear Actuators”, Chemistry Letters, Japan, Vol. 32, 2003 No., p 576-577. J. et al. M.M. Sansinena et al., Chem. Commun. , P2217-2218, 1997.

  Accordingly, an object of the present invention is to provide a polymer actuator element exhibiting an excellent expansion / contraction rate and response speed in an open system at room temperature and normal pressure. Moreover, the objective of this invention is providing the manufacturing method and drive method of the said polymer actuator element.

  In order to achieve the above object, the present inventors have intensively studied the configuration of the polymer actuator element. As a result, they have found that the above-described problems can be solved by using the following method, and have completed the present invention.

That is, the polymer actuator element of the present invention is a polymer actuator element containing a conductive polymer and a driving electrolyte,
The driving electrolyte is a solution containing a nonionic organic compound that is liquid at normal temperature and pressure.

  According to the present invention, as shown in the results of the examples, a polymer actuator element excellent in expansion and contraction rate and response speed can be obtained by using a solution containing a nonionic organic compound that is liquid at normal temperature and pressure as the driving electrolyte. It becomes. Although the details of the reason why the polymer actuator element exhibits such characteristics are not clear, the diffusibility, viscosity, ease of ion dissociation, dielectric constant, etc. of the nonionic organic compound act in a balanced manner. It is presumed that the present invention has an excellent effect. Further, in the present invention, even when the same driving performance as that of the prior art is exhibited, the driving voltage can be set lower than that of the prior art.

  In the (electrolyte) driving electrolyte solution in the conventional polymer actuator element, a nonionic organic compound, particularly a nonionic polymer compound, has never been used as an electrolyte medium. This is because a nonionic organic compound is used as a medium (electrolyte medium), so that the affinity with the conductive polymer is low, and the molecular chain of the polymer compound is entangled with the polymer electrolyte (ion exchange resin). This is because the movement of electrolytes such as ions is hindered by the high molecular weight medium. Furthermore, it has been difficult to fill the conductive polymer or the like with a nonpolar compound. However, in the present invention, by using the polymer actuator element containing the nonionic organic compound, by using the driving electrolyte as described above, an excellent stretch rate and response speed in an open system at normal temperature and pressure. It has been found that the polymer actuator element exhibits the following.

  The polymer actuator element preferably includes a composite film in which the conductive polymer is disposed on both surfaces of a porous substrate via a metal electrode layer, and more specifically, for example, A bimorph type polymer actuator element including a composite film in which a porous support is laminated in the center in the order of a metal electrode layer and a conductive polymer can be obtained. The bimorph type polymer actuator element can convert the expansion / contraction behavior of the conductive polymer actuator in the same direction to the movement in the bending direction of the structure. Therefore, the expansion / contraction behavior of the polymer actuator element of the present invention can be improved more efficiently. It can be expressed as a large bending deformation. In addition, the bimorph type polymer actuator element has an excellent stretching rate even in an open system at normal temperature and pressure without immersing the polymer actuator element in the electrolyte solution during driving by impregnating the composite membrane with the electrolyte solution. And is particularly suitable for use as an air-driven polymer actuator element that exhibits a response speed.

  From the viewpoint of electrical properties and durability, the porous substrate is preferably porous polytetrafluoroethylene.

  In the present invention, the nonionic organic compound is preferably an organic compound having a boiling point or a decomposition temperature of 180 ° C. or higher. By using such an organic compound, it is possible to obtain a polymer actuator element in which deterioration of responsiveness with time is more effectively suppressed.

  In the present invention, it is preferable that the freezing point or softening point of the nonionic organic compound is 0 ° C. or lower. By using these nonionic organic compounds, even when the outside air is 0 ° C. or less, it can be driven more reliably for a long period of time.

  Furthermore, in the present invention, the nonionic organic compound is preferably a polyether compound such as polyethylene glycol, polypropylene glycol, and / or a similar compound thereof. By using these nonionic organic compounds, especially polyether compounds, in an open system at room temperature and normal pressure, the initial bending amount or displacement amount can be maintained for a longer period without being greatly affected by the humidity of the outside air. Will be able to do.

  In the present invention, the driving electrolyte may further contain an ionic liquid. By using the ionic liquid, the initial bending amount or displacement amount can be maintained for a longer period in an open system at room temperature and normal pressure without being particularly affected by the humidity of the outside air.

As the ionic liquid,
A cation selected from at least one selected from the group consisting of tetraalkylammonium ion, dialkylimidazolium ion, trialkylimidazolium ion, pyrazolium ion, pyrrolium ion, pyrrolium ion, pyrrolidinium ion, and piperidinium ion;
PF ₆ ⁻ , BF ₄ ⁻ , AlCl ₄ ⁻ , ClO ₄ ⁻ , and the following formula (I)
It is preferable to include a salt composed of a combination with at least one anion selected from the group consisting of sulfonium imide anions represented by formula (1).
_{(C m F (2m + 1} ) SO 3) (C n F (2n + 1) SO 2) N - (I)
[In the above formula (I), m and n are arbitrary integers. ].

  Furthermore, the conductive polymer preferably contains pyrrole and / or a pyrrole derivative in the molecular chain.

Further, the conductive polymer is a film-shaped conductive polymer doped with perfluoroalkylsulfonylimide ions represented by the following formula (1):
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ],
Or a film-like conductive polymer doped with perfluoroalkylsulfonylmethide ion represented by the following formula (2):
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ],
Is preferred.

  In the polymer actuator element of the present invention, the conductive polymer may have an expansion / contraction rate per oxidation-reduction cycle of 5% or more.

  In the polymer actuator element of the present invention, the response frequency of the polymer actuator element may be 100 Hz or more.

On the other hand, the method for producing a polymer actuator element of the present invention includes a polymer actuator element comprising a conductive polymer and a driving electrolyte solution, wherein the driving electrolyte solution is a solution containing a liquid nonionic organic compound at normal temperature and pressure. A manufacturing method of
A first step of immersing the conductive polymer in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under a normal temperature and a normal pressure; and
A second step of removing the polar solvent from the conductive polymer;
It is characterized by including.

The method for producing a polymer actuator element according to the present invention includes a composite film in which the conductive polymer is disposed on both surfaces of a porous base material via metal electrode layers, and a driving electrolyte solution. A manufacturing method of
A first step of immersing the composite membrane in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under normal temperature and normal pressure; and
A second step of removing the polar solvent from the composite membrane;
It is characterized by including.

  Since the method for producing a polymer actuator element of the present invention includes the steps as described above, it can be efficiently and simply filled with a driving electrolyte containing a nonionic organic compound, which has been difficult in the past. A polymer actuator element excellent in rate and response speed can be easily produced.

  On the other hand, the driving method of the polymer actuator element of the present invention includes a step of applying a voltage between the metal electrodes of any of the polymer actuator elements described above.

  The polymer actuator element of the present invention can be easily used for a wide variety of practical applications as a polymer actuator that generates displacement or bending displacement. In particular, the polymer actuator element is suitable for applications that require driving with excellent stretch rate and response speed in an open system at room temperature and normal pressure. Furthermore, since the actuator element does not require complicated mechanical parts, the apparatus used can be easily reduced in size and weight. Furthermore, the actuator element can be an actuator that generates a linear displacement by combining the actuator element with a device that converts a bending motion into a linear motion. An actuator that generates a linear displacement or a bending displacement can be used as a driving unit that generates a linear driving force or a driving unit that generates a driving force for moving a track-type orbit made of an arc portion. . Further, the actuator element can be used as a pressing portion that performs a linear operation.

  Hereinafter, embodiments of the present invention will be described in detail.

The polymer actuator element of the present invention is a polymer actuator element containing a conductive polymer and a driving electrolyte,
The driving electrolyte is a solution containing a nonionic organic compound that is liquid at normal temperature and pressure.

(Drive electrolyte)
The driving electrolyte used in the present invention includes an electrolyte for driving the polymer actuator element by applying a voltage, and is used as a solvent for dissolving the electrolyte. In the present invention, a solution containing a nonionic organic compound that is liquid at normal temperature and pressure can be used as a solvent for dissolving the electrolyte. By including the above solution as the driving electrolyte, the polymer actuator element can exhibit a large driving speed when the amount of expansion and contraction (driving speed) with respect to time in a state where a constant voltage is applied is measured.

  The polymer actuator element contains a nonionic organic compound that is liquid at room temperature and normal pressure, particularly a liquid organic compound or polyether compound that has a boiling point or decomposition temperature of 180 ° C. or higher and is liquid at room temperature and normal pressure. Therefore, even in an open system at room temperature and normal pressure, the bending amount or the displacement amount of the actuator element hardly changes over time. Therefore, the polymer actuator element can be driven outside the solution, that is, in the open air, and is suitable for long-term driving because there is almost no evaporation of the electrolyte medium solution.

  The nonionic organic compound is not particularly limited as long as it does not have an ionic functional group or ionic moiety in the molecular structure, and can be used as appropriate. The organic compound may be any organic compound that can serve as a salt solvent containing ions that serve as charge carriers, or any organic compound that can serve as charge carriers.

  The nonionic organic compound has a boiling point or decomposition temperature of 180 ° C. or higher, is preferably liquid at normal temperature and pressure, and preferably has a function as a solvent. Further, an organic solvent having a boiling point of 245 ° C. or higher is more preferable. These compounds may be used alone or in combination of two or more.

  In the present invention, it is preferable that the freezing point or softening point of the nonionic organic compound is 0 ° C. or lower. By using these nonionic organic compounds, even when the outside air is 0 ° C. or less, it can be driven more reliably for a long period of time.

  Examples of the nonionic organic compound include diethylene glycol, glycerin, sulfolane, propylene carbonate, butyrolactone, and polyether compounds. Among these, for example, diethylene glycol, glycerin, sulfolane, polyether compounds, and the like are preferable. Furthermore, the use of a polyether compound is particularly preferable because long-term durability can be obtained with well-balanced driving performance.

  Moreover, the said polyether compound will not be specifically limited if it is a liquid under normal temperature normal pressure. The polyether compound preferably has a function as a solvent. The polyether compound may be any polyether compound that can serve as a salt solvent containing ions that serve as charge carriers, or any polyether compound that can serve as charge carriers. These polyether compounds may be used alone or in combination of two or more.

  The polyether compound is not particularly limited as long as it is a compound having an ether structure as a repeating unit, such as an alkylene oxide (oxyalkylene) unit, among which an ethylene oxide (oxyethylene) unit or a propylene oxide (oxygen) More preferred is a compound having propylene) or the like as a repeating unit.

  Examples of the polyether compound include those having a structure in which the number of added moles (number of repeating units) of an oxyalkylene unit such as an alkylene oxide (oxyalkylene) unit is repeated by 3 units or more. Examples thereof include homopolymers and copolymers having molecular weights, compounds containing these polymer structures, analogs thereof, ether type surfactants, and ether type plasticizers.

  More specifically, examples of the polyether compound include polyethylene glycol, polypropylene glycol, polyalkylene glycol such as polyethylene glycol and polypropylene glycol copolymer (polyoxyethylene polyoxypropylene glycol), and polyoxyethylene lauryl sulfate. Examples include triethanolamine, sodium polyoxyethylene lauryl sulfate, polyoxyethylene methyl glucoside, polyethylene glycol di-2-ethyl hexaate, tetraethylene glycol-2-ethyl hexaate, polyetherol compounds, and analogs thereof. . Among these, it is particularly preferable to use polyethylene glycol, polypropylene glycol, and / or related compounds thereof.

  More specifically, examples of the polyalkylene glycol include, for example, polyethylene glycol, polypropylene glycol, and a polypropylene glycol copolymer (polyoxyethylene polyoxypropylene glycol) such as polypropylene glycol-polyethylene glycol-polypropylene glycol. Examples thereof include a block copolymer, a block copolymer of polypropylene glycol-polyethylene glycol, a block copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol, and a random copolymer of polypropylene glycol-polyethylene glycol. Further, the end of the glycol chain may be a hydroxyl group or may be substituted with an alkyl group, a phenyl group or the like. These compounds may be used alone or in combination of two or more.

  Examples of the ether surfactant include polyoxyalkylene alkyl ether sulfates such as polyoxyethylene lauryl sulfate triethanolamine and polyoxyethylene lauryl sodium sulfate. These compounds may be used alone or in combination of two or more.

  The added mole number (number of repeating units) of the oxyalkylene unit of the polyether compound is preferably 3 to 100, more preferably 4 to 80, and more preferably 5 to 10 from the viewpoint of interaction with ions. When the added mole number of the oxyalkylene unit is less than 3, it may be difficult to maintain the driving performance over time because the volatility of the medium in the electrolyte increases and the hygroscopicity decreases.

  The molecular weight of the polyether compound-containing compound is not particularly limited as long as it is liquid at room temperature and normal pressure, but those having a number average molecular weight of 1000 or less are suitably used, those having 200 to 800 are more suitably used, The thing of 300-600 is used more suitably. When the number average molecular weight exceeds 1000, it may be solidified under normal temperature and pressure, which is not preferable. The number average molecular weight is obtained by measuring by GPC (gel permeation chromatography).

  The nonionic organic compound may be used singly or in combination of two or more, but the blending amount is 0.01 to 100 weights with respect to 100 parts by weight of the electrolytic solution. Parts, preferably 0.05 to 50 parts by weight, more preferably 0.1 to 30 parts by weight. If the amount is less than 0.01 parts by weight, sufficient durability over time may not be obtained, and if the amount exceeds 100 parts by weight, the drive frequency may decrease.

  In particular, when the above polyether compound is used, the above polyether compound may be used alone, or two or more kinds may be mixed and used. The amount is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 0.1 to 1 part by weight with respect to parts. If it is less than 0.01 part by weight, sufficient durability cannot be obtained, and if it exceeds 10 parts by weight, the polyether compound may bleed. By including the polyether compound in the electrolyte, even if the polymer actuator element is not sealed, a response drive of 100 Hz or more can be performed after one month.

Further, the driving electrolyte contains an anion as an electrolyte. The anion can use trifluoromethanesulfonic acid ions, BF ₄ ⁻ , PF ₆ ⁻ or perfluoroalkylsulfonylimide ions as dopant ions. In addition, as the anion, for example, an electrolyte salt that forms a counter ion with a cation with Na ⁺ , K ⁺ , Li ^+, or the like may be used.

  Examples of the electrolyte salt include lithium salts, sodium salts, potassium salts, and the like of the anions. Among them, lithium perfluoroalkylsulfonylimide is preferable.

  When an electrolyte salt is added as the electrolyte, the electrolyte salt is preferably included in an amount of 1 to 90 parts by weight, more preferably 5 to 75 parts by weight, with respect to 100 parts by weight of the driving electrolyte. It is particularly preferable that 50 parts by weight is contained.

  In the present invention, the driving electrolyte may further contain an ionic liquid. By using the ionic liquid, the initial bending amount or displacement amount can be maintained for a longer period in an open system at room temperature and normal pressure without being particularly affected by the humidity of the outside air.

  The ionic liquid is also called a room temperature molten salt and has almost no vapor pressure at room temperature (about 25 ° C.). Therefore, the polymer actuator element of the present invention in which the polymer electrolyte is swollen with the polyether compound and the ionic liquid can bend or displace substantially the same as the initial state even for a long period of about several months. .

The ionic liquid can be used without any particular limitation. Among these, the ionic liquid is composed of imidazolium ions such as tetraalkylammonium ions, dialkylimidazolium ions, trialkylimidazolium ions, pyrazolium ions, pyrrolium ions, pyrrolium ions, pyrrolidinium ions, and piperidinium ions. At least one cation selected from the group consisting of PF ₆ ⁻ , BF ₄ ⁻ , AlCl ₄ ⁻ , ClO ₄ ⁻ , and at least one anion selected from the group consisting of sulfonium imide anions represented by the following formula (I): It is preferable that the salt which consists of a combination of these is included. These ionic liquids may be used alone or in combination of two or more.
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 3) N - (I)
[In the above formula (I), m and n are arbitrary integers. ].

  Examples of the tetraalkylammonium ion include trimethylpropylammonium, trimethylhexylammonium, tetrapentylammonium, and the like.

  Examples of the imidazolium cation include a dialkyl imidazolium ion and / or a trialkyl imidazolium ion. More specifically, examples of the imidazolium cation include 1-ethyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, and 1-hexyl. -3-methylimidazolium ion, 1,3-dimethylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium Ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl-2,3-dimethylimidazolium ion, and the like.

  Examples of the alkylpyridinium ion include N-methylpyridinium ion, N-ethylpyridinium ion, N-propylpyridinium ion, N-butylpyridinium ion, 1-ethyl-2-methylpyridinium ion, and 1-butyl-4-methyl. Examples thereof include pyridinium ions and 1-butyl-2,4-dimethylviridinium ions.

  Examples of the pyrrolium cation include 1,1-dimethylpyrrolium ion, 1-ethyl-1-methylpyrrolium ion, 1-methyl-1-propylpyrrolium ion, 1-butyl-1-methylpyrrolium ion, and the like. Can do.

  Examples of the pyrazolium cation include 1,2-dimethylpyrazolium ion, 1-ethyl-2-methylpyrazolium ion, 1-propyl-2-methylpyrazolium ion, and 1-butyl-2-methylpyrazolizion. Um ion etc. can be raised.

  Examples of the pyrrolium cation include 1,2-dimethylpyrrolium ion, 1-ethyl-2-methylpyrrolium ion, 1-propyl-2-methylpyrrolium ion, and 1-butyl-2-methylpyrrolium ion. Etc.

  Examples of the pyrrolidinium cation include 1,1-dimethylpyrrolidinium ion, 1-ethyl-1-methylpyrrolidinium ion, 1-methyl-1-propylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium. Um ion etc. can be raised.

  Examples of the piperidinium cation include 1,1-dimethylpiperidinium ion, 1-ethyl-1-methylpiperidinium ion, 1-methyl-1-propylpiperidinium ion, 1-butyl-1-methylpipe. Lizinium ions can be used.

In the ionic liquid, the combination of the anion and the cation is not particularly limited. For example, 1-methyl-3-ethylimidazolium trifluoromethanesulfimide (EMITFSI), 1-methyl-3-imidazo Rium tetrafluoroborate (EMIBF ₄ ), 1-methyl-3-imidazolium hexafluorophosphoric acid (EMIPF ₆ ), trimethylpropylammonium trifluoromethanesulfonimide, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1- Hexyl-3-methylimidazolium hexafluorophosphoric acid, 1-hexyl-3-methylimidazolium trifluoromethanesulfonimide, or the like can be used.

  In the polymer actuator element of the present invention, the polymer electrolyte contains the nonionic organic compound, particularly the polyether compound, and the ionic liquid, so that it can be used at atmospheric pressure (normal temperature or normal pressure or 0 ° C. or less). The polymer actuator element can be driven even after being left for about 1000 hours.

  The ionic liquid may be used alone, or two or more kinds may be mixed and used. When the ionic liquid is used in combination, the amount of the ionic liquid used is the driving electrolyte. In 100 parts by weight of the solution, the ionic liquid is preferably 2 to 80% by weight, more preferably 10 to 60% by weight, and further preferably 20 to 50% by weight. If it is less than 2% by weight, the effect of addition may not be sufficiently selected, and if it exceeds 80% by weight, bleed out (separation and precipitation of ionic liquid (ionic fluid)) may occur.

Furthermore, in order to obtain a higher driving speed in the driving electrolyte, a perfluoroalkylsulfonylimide ion represented by the following formula (1) is contained in the bulk of the conductive polymer contained in the polymer actuator element. It is more preferable that the driving electrolyte contains a perfluoroalkylsulfonylimide ion represented by the following formula (1).
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ].

Further, in order to obtain a higher driving speed in the driving electrolyte, perfluoroalkylsulfonylmethide ion represented by the following formula (2) is contained in the bulk of the conductive polymer contained in the polymer actuator element. It is more preferable that the driving electrolyte contains a perfluoroalkylsulfonylmethide ion represented by the following formula (2).
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ].

  By containing these dopant ions, the perfluoroalkylsulfonylimide or perfluoroalkylsulfonylmethide ion is taken into or released from the bulk of the conductive polymer, and the conductive polymer has a large stretching motion. Therefore, the polymer actuator element can exhibit a higher driving speed than the conventional electroconductive polymer electrostretching method.

  In the polymer actuator element of the present invention, the working electrolyte contains the same anion as the anion contained in the conductive polymer tangible material having a specific shape and containing the conductive polymer. It is preferred that The conductive electrolyte used in the polymer actuator element contains the same anion as the anion that can function as a dopant in the working electrolyte solution. Therefore, it is possible to easily obtain a desired amount of electrolytic expansion / contraction. In addition, when the anion contained in the driving electrolyte is perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion, production of a conductive polymer tangible material that causes electrolytic stretching in the driving electrolyte It is preferable that the ionic radius is the same as that of perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion contained in the electrolyte for electrolysis because the electrolytic expansion and contraction can be easily performed.

(Polymer actuator element)
The polymer actuator element of the present invention is particularly limited as long as it contains the above-described driving electrolyte and contains a conductive polymer that can be driven by electrolytic expansion and contraction by applying a voltage. It is not something.

  The conductive polymer is not particularly limited in shape as a bulk, but is a film-like body, a cylindrical body, a cylindrical body, a polygonal columnar body such as a prismatic or hexagonal column, a conical body, or a plate-shaped body. Any specific shape such as a rectangular parallelepiped may be used. When the conductive polymer constitutes a part or the whole of the polymer actuator element as a tangible object having a specific shape, the conductive polymer can be easily driven by electrolytic expansion and contraction by applying voltage to the conductive polymer. can do.

  As the shape of the polymer actuator element, besides the above shape, it can be appropriately formed into a shape suitable for the use situation. Moreover, components, such as a protection member, can be added to the shape of the polymer actuator element of this invention, and it can be set as a desired shape. For the polymer actuator element, the conductive polymer film obtained on the working electrode by electrolytic polymerization may be used as it is, or may be formed into a desired shape by forming such as lamination. Furthermore, the counter electrode is not limited to a columnar shape, and may be a plate shape or the like.

The conductive polymer is not particularly limited as long as the conductive polymer can be doped and dedoped with an anion as a dopant. As the dopant, trifluoromethanesulfonic acid ion, BF ₄ ⁻ , PF ₆ ⁻ , perchloric acid ion or perfluoroalkylsulfonylimide ion can be used according to the required amount of electrolytic expansion and contraction, application, and the like.

In particular, as the conductive polymer, the conductive polymer is a film-shaped conductive polymer doped with perfluoroalkylsulfonylimide ions represented by the following formula (1):
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ],
Alternatively, as the conductive polymer, a film-shaped conductive polymer doped with perfluoroalkylsulfonylmethide ion represented by the following formula (2) is used.
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ],
However, it is preferable because a higher driving speed can be obtained.

  As described above, the conductive polymer containing perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion in the bulk can also exhibit a large expansion / contraction rate per one oxidation-reduction cycle. These anions have a larger molecular size than conventional dopants such as trifluoromethanesulfonate ions. Therefore, perfluoroalkylsulfonylimide ions or perfluoroalkylsulfonylmethide ions are present inside a tangible material of a conductive polymer having a predetermined shape, but by repeatedly switching the applied voltage between positive and negative. It is speculated that these larger molecular-size anions enter and exit the conductive polymer tangible material, and as a result, can perform large electrolytic expansion and contraction per one redox cycle.

In the perfluoroalkylsulfonylimide ion, a sulfonyl group is bonded to a nitrogen atom that is the center of an anion, and further, there are two perfluoroalkyl groups that are substituents. One of the perfluoroalkylsulfonyl groups is represented by C _n F _{(2n + 1)} SO ₂ , and the other perfluoroalkylsulfonyl group is represented by C _m F _{(2m + 1)} SO ₂ .

  The above m and n are each an arbitrary integer of 1 or more, and m and n may be the same integer, or n and m may be different integers. For example, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, etc. it can. Examples of the perfluoroalkylsulfonylimide salt include bis (trifluoromethylsulfonyl) imide salt, bis (pentafluoroethylsulfonyl) imide salt, and bis (heptadecafluorooctylsulfonyl) imide salt.

The perfluoroalkylsulfonylmethide ion has a sulfonyl group bonded to the carbon atom that is the center of the anion, and further has two perfluoroalkyl groups that are substituents. One of the perfluoroalkylsulfonyl groups is represented by C _n F _{2n + 1} SO ₂ , and the other perfluoroalkylsulfonyl group is represented by C _m F _{2m + 1} SO ₂ , and further C _l F _{21 + 1} SO ₂ .

  The above-mentioned l, m, and n are each an arbitrary integer of 1 or more, and l, m, and n may be the same integer, and l, m, and n may be different integers. For example, trifluoromethylsulfonyl group, pentafluoroethylsulfonyl group, heptafluoropropylsulfonyl group, nonafluorobutylsulfonyl group, undecafluoropentylsulfonyl group, tridecafluorohexylsulfonyl group, pentadecafluoroheptylsulfonyl group, heptadecafluoro Examples thereof include an octylsulfonyl group. Examples of the perfluoroalkylsulfonylmethide salt include tris (trifluoromethylsulfonyl) methide salt, tris (pentafluoroethylsulfonyl) methide salt, and tris (heptadecafluorooctylsulfonyl) methide salt. Among them, as an aspect of the present invention, the trimeth (trifluoromethylsulfonyl) methide ion in which the above metide ion is 1 = 1 in the above formula 1, m = 1, n = 1, or n = 1 in the above formula 3 is used. preferable.

In addition, the said conductive polymer can also contain the other anion which can dope and dedope this conductive polymer as an anion as a dopant. For example, trifluoromethanesulfonic acid ions, BF ₄ ⁻ , PF ₆ ⁻ , perchloric acid ions, perfluoroalkylsulfonylimide ions, or the like can be used depending on the required amount of electrolytic expansion and contraction, usage, and the like.

  Further, the perfluoroalkylsulfonylimide ion of the above chemical formula (1) and the perfluoroalkylsulfonylmethide ion of the above chemical formula (2) can form a salt with a cation, and a perfluoroalkylsulfonylimide salt or a perfluoroalkyl A sulfonylmethide ion salt may be added to the electrolytic solution in the electrolytic polymerization method.

The cations that form salts with these perfluoroalkylsulfonylimide ions or perfluoroalkylsulfonylmethide ions may be composed of one element such as Li ⁺ , or may be composed of a plurality of elements. The cation is not particularly limited as long as it is a Lewis acid capable of forming a perfluoroalkylsulfonylimide salt or a perfluoroalkylsulfonylmethide salt as a monovalent cation and dissociating in an electrolyte. Is not to be done.

  The conductive polymer can be easily obtained by an electrolytic polymerization method or the like. The conductive polymer is a conductive polymer obtained by an electrolytic polymerization method, and an electrolytic solution (electrolytic solution for producing a conductive polymer) used for the electrolytic polymerization is an ether bond, an ester bond, a carbonate. It is preferable that an organic compound and / or a halogenated hydrocarbon containing at least one bond or functional group among a bond, a hydroxyl group, a nitro group, a sulfone group, and a nitrile group be included as a solvent. By including the above-mentioned solvent in the above electrolytic solution and further including perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion, the obtained conductive polymer is larger in one redox cycle. It shows electrolytic expansion and contraction.

  Examples of the organic compound include 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane (an organic compound containing an ether bond), γ-butyrolactone, Ethyl acetate, n-butyl acetate, t-butyl acetate, 1,2-diacetoxyethane, 3-methyl-2-oxazolidinone, methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, diethyl phthalate ( Above, organic compounds containing ester bonds), propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate (above, organic compounds containing carbonate bonds), ethylene glycol, butanol, 1-hexanol, cyclohexano 1-octanol, 1-decanol, 1-dodecanol, 1-octadecanol (above, organic compound containing hydroxyl group), nitromethane, nitrobenzene (above, organic compound containing nitro group), sulfolane, dimethylsulfone (above) , An organic compound containing a sulfone group), and acetonitrile, butyronitrile, benzonitrile (an organic compound containing a nitrile group). The organic compound containing a hydroxyl group is not particularly limited, but is preferably a polyhydric alcohol or a monohydric alcohol having 4 or more carbon atoms because of its high expansion / contraction ratio. In addition to the above examples, the organic compound may have any two or more bonds or functional groups among the ether bond, ester bond, carbonate bond, hydroxyl group, nitro group, sulfone group and nitrile group in the molecule. The organic compound contained in the combination may be sufficient.

  In addition, the halogenated hydrocarbon contained as a solvent in the electrolytic solution for producing a conductive polymer is one in which at least one hydrogen in the hydrocarbon is substituted with a halogen atom, and is stably present as a liquid under electrolytic polymerization conditions. If it can do, it will not specifically limit. Examples of the halogenated hydrocarbon include dichloromethane and dichloroethane. Although only one kind of the halogenated hydrocarbon can be used as a solvent in the electrolytic solution for producing the conductive polymer, two or more kinds can be used in combination. The halogenated hydrocarbon may be used as a mixed solution with the organic compound, or a mixed solvent with the organic solvent may be used as a solvent in the electrolytic solution for producing the conductive polymer.

  In the bulk of the conductive polymer obtained by the electrolytic polymerization method, the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion used in the electrolytic polymerization method is present. The conductive polymer in which the conductive polymer contains the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion has a large expansion / contraction amount per one oxidation-reduction cycle as described above, and the driving speed (% / The value of s) is also large, and it is preferable because it can be easily obtained. For example, in the case of a film-like body of the above-described conductive polymer tangible material, the maximum expansion rate of conventional electroconductive polymer electrostriction can be obtained up to about 10 to 15% per oxidation-reduction cycle in the surface direction. In contrast, the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion is included as a dopant in the bulk of the conductive polymer, so that 16% per oxidation-reduction cycle in the lengthwise direction. As described above, an excellent maximum expansion / contraction rate of 20% or more can be exhibited. The film-like body can be suitably used for applications requiring a large expansion / contraction rate typified by artificial muscle. In addition to the dopant, the conductive polymer tangible material may appropriately include a conductive material such as a metal wire or a conductive oxide in order to reduce the resistance value as the working electrode.

  Similarly to the above description, the perfluoroalkylsulfonylimide ion only needs to have a sulfonyl group bonded to the nitrogen atom that is the center of the anion, and further has two perfluoroalkyl groups that are substituents. For example, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group and the like can be mentioned. . Examples of the perfluoroalkylsulfonylimide salt include bis (trifluoromethylsulfonyl) imide salt, bis (pentafluoroethylsulfonyl) imide salt, and bis (heptadecafluorooctylsulfonyl) imide salt.

  In addition, the perfluoroalkylsulfonylmethide ion, as described above, has a sulfonyl group bonded to a carbon atom which is an anion center, and further has three perfluoroalkyl groups which are substituents. Good. For example, trifluoromethylsulfonyl group, pentafluoroethylsulfonyl group, heptafluoropropylsulfonyl group, nonafluorobutylsulfonyl group, undecafluoropentylsulfonyl group, tridecafluorohexylsulfonyl group, pentadecafluoroheptylsulfonyl group, heptadecafluoro Examples thereof include an octylsulfonyl group. Examples of the perfluoroalkylsulfonylmethide salt include tris (trifluoromethylsulfonyl) methide salt, tris (pentafluoroethylsulfonyl) methide salt, and tris (heptadecafluorooctylsulfonyl) methide salt.

The perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion that may be contained in the electrolytic solution of the electrolytic polymerization method can form a salt with a cation, and the perfluoroalkylsulfonylimide salt or perfluoroalkylsulfonyl It may be added as a methide salt in the electrolytic solution in the electrolytic polymerization method. The cation that forms a salt with the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion may be composed of one element, such as Li ⁺ , or may be composed of a plurality of elements. The cation is not particularly limited as long as it is a Lewis acid capable of forming a perfluoroalkylsulfonylimide ion as a monovalent cation and dissociating in an electrolyte.

  When the cation is a metal element, for example, an element selected from alkali metals such as lithium can be used. Moreover, when the cation is a molecule, for example, tetrabutylammonium, alkylammonium typified by tetraethylammonium, pyridinium, imidazolium, or the like can be used.

  The perfluorosulfonylimide ion that can be used as a dopant for the conductive polymer forms various salts by the combination of the perfluoroalkylsulfonylimide ion that is the base component and the cation that is the acid component as described above. However, since perfluorosulfonylimide salts are easily dissociated in solution and easily available, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, etc. Tetrabutylammonium for lithium bis (perfluoroalkylsulfonyl) imide and bis (perfluoroalkylsulfonyl) imide such as bis (trifluoromethylsulfonyl) imide and bis (pentafluoroethylsulfonyl) imide Umushio, pyridinium salts or imidazolinium indium salts are preferred.

  The perfluoroalkylsulfonylmethide ion, which can be used as a dopant for the conductive polymer, has various salts depending on the combination of the perfluoroalkylsulfonylmethide ion as the base component and the cation as the acid component as described above. However, since perfluorosulfonylmethide salt is easily dissociated in solution and easily available, lithium tris (trifluoromethylsulfonyl) methide, lithium tris (pentafluoroethylsulfonyl) ) For lithium tris (perfluoroalkylsulfonyl) methides such as methide, and tris (perfluoroalkylsulfonyl) methides such as tris (trifluoromethylsulfonyl) methide and tris (pentafluoroethylsulfonyl) methide Tetrabutylammonium salt, pyridinium salt or imidazolium indium salts are preferred.

  The content of the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion in the electrolytic polymerization method in the electrolytic solution is not particularly limited, but in order to ensure sufficient ionic conductivity of the electrolytic solution. The perfluoroalkylsulfonylimide salt is preferably contained in the electrolytic solution in an amount of 1 to 40% by weight, and more preferably 2.8 to 20% by weight. Moreover, in order to improve the film quality of the conductive polymer film obtained by the electrolytic polymerization method, a composite electrolyte in which 1 to 80% of trifluoromethanesulfonate is added to the electrolytic solution can also be used. Moreover, these ions may be used alone or in combination of two or more.

  In addition, the electrolytic solution (electrolytic solution for producing a conductive polymer) used in the electrolytic polymerization method further contains a monomer of a conductive polymer in addition to the perfluoroalkylsulfonylimide salt. In addition, other known additives such as polyethylene glycol and polyacrylamide may also be included.

As the electropolymerization method, a known electropolymerization method can be used as the electropolymerization of the conductive polymer monomer, and any of the constant potential method, the constant current method, and the electric sweep method can be appropriately used. it can. For example, the electrolytic polymerization method can be performed at a current density of 0.01 to 20 mA cm ⁻² and a reaction temperature of −70 to 80 ° C. In order to obtain a conductive polymer having a good film quality, a current density of 0.1 It is preferable to carry out under the conditions of ˜2 mA cm ⁻² and the reaction temperature of −40 to 40 ° C., and the reaction temperature is more preferably −30 to 30 ° C.

  In addition, the working electrode used for the said electrolytic polymerization method will not be specifically limited if it can be used for electrolytic polymerization, An ITO glass electrode, a carbon electrode, a metal electrode, etc. can be used suitably. The metal electrode is not particularly limited as long as it is an electrode mainly composed of metal, but a metal for a metal element selected from the group consisting of Pt, Ti, Ni, Au, Ta, Mo, Cr and W. A single electrode or an alloy electrode can be preferably used. Among them, the metal species contained in the metal electrode is particularly preferably Pt or Ti because the obtained conductive polymer has a large expansion / contraction rate and generation force and the electrode can be easily obtained. As the above alloy, for example, trade names “INCOLOY alloy 825”, “INCONEL alloy 600”, “INCONEL alloy X-750” (manufactured by Daido Special Metal Co., Ltd.) can be used. As the counter electrode, a known electrode such as Pt or Ni can be preferably used.

  The monomer of the conductive polymer contained in the electrolytic solution used in the above electrolytic polymerization method is not particularly limited as long as it is a compound that is polymerized by oxidation by electrolytic polymerization and exhibits conductivity. For example, pyrrole , Hetero five-membered cyclic compounds such as thiophene and isothianaphthene, and derivatives such as alkyl groups and oxyalkyl groups thereof. Of these, hetero five-membered cyclic compounds such as pyrrole and thiophene, and derivatives thereof are preferable, and in particular, a conductive polymer containing pyrrole and / or a pyrrole derivative is easy to produce, and as a conductive polymer. It is preferable because it is stable. These compounds may be used alone or in combination of two or more.

  In addition, the polymer actuator element preferably includes a composite film in which the conductive polymer is disposed on both surfaces of the porous substrate via metal electrode layers, respectively, more specifically, For example, as shown in FIG. 1, a bimorph type high structure including a composite film in which a porous support (base material layer 10) is sandwiched in the order of a metal electrode layer 12 and a conductive polymer 14 in the center. It can be a molecular actuator element. The bimorph type polymer actuator element can convert the expansion / contraction behavior of the conductive polymer actuator in the same direction to the movement in the bending direction of the structure. Therefore, the expansion / contraction behavior of the polymer actuator element of the present invention can be improved more efficiently. It can be expressed as a large bending deformation. In addition, the bimorph type polymer actuator element is obtained by impregnating the composite film (especially in a porous substrate) with an electrolyte solution, so that the polymer actuator element is not immersed in the electrolyte solution during driving at normal temperature and normal pressure. It is particularly suitable for use as an air-driven polymer actuator element that exhibits excellent stretch rate and response speed even in an open system.

  As the base material layer sandwiched on both sides of the metal electrode layer of the composite film, for example, a porous base material (porous support) such as polytetrafluoroethylene (PTFE), polyamide, polyolefin, and cellulose acetate is preferable. Among them, as the porous substrate (porous support), porous polytetrafluoroethylene (porous PTFE) is used from the viewpoint of chemical stability and softness and durability in repeated driving of the polymer actuator element. It is particularly preferable to use When driven in the air, the layer holding the electrolyte (porous substrate layer (porous support layer)) preferably has a high ionic conductivity, and the porosity is as high as possible. Higher is preferred.

  As the metal electrode layer, gold, platinum, copper, nickel, or the like can be used, and among them, gold, platinum, and the like are preferable.

  In particular, in a bimorph type polymer actuator element, it is preferable from the viewpoint of maintaining a long-term driving performance that the conductive polymer is polymerized and firmly integrated on the metal electrode layer.

  In the polymer actuator element, the thickness of the conductive polymer is preferably 0.01 to 10 μm, and more preferably 0.1 to 2 μm.

  Further, the thickness of the polymer actuator element is preferably 0.5 to 50 μm, and more preferably 1 to 30 μm. In particular, in a bimorph type polymer actuator element, the thickness of the polymer actuator element is preferably 1 to 100 μm, and more preferably 10 to 60 μm.

  The polymer actuator element in the present invention has the above-described configuration. A tangible object having a desired shape is constituted by the conductive polymer, the tangible object constitutes all or part of the polymer actuator element, and the tangible object drives to drive the polymer actuator element. To do. The shape of the conductive polymer tangible material is not particularly limited, and may be formed or molded into a film shape, a tubular shape, a tubular shape, a prismatic shape, a fibrous shape, or the like. Since the conductive polymer is obtained as a film on the working electrode during the electropolymerization, it is preferable that the conductive polymer is a film or can be applied in the form of a film. Further, the conductive polymer polymerized on the working electrode is separated from the working electrode using a solvent capable of swelling the conductive polymer such as acetone. Can be easily obtained.

(Manufacturing method of polymer actuator element)
The method for producing a polymer actuator element of the present invention comprises producing a polymer actuator element comprising a conductive polymer and a driving electrolyte, wherein the driving electrolyte is a solution containing a liquid nonionic organic compound at normal temperature and pressure. A method,
A first step of immersing the conductive polymer in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under a normal temperature and a normal pressure; and
A second step of removing the polar solvent from the conductive polymer;
It is characterized by including.

The method for producing a polymer actuator element according to the present invention includes a composite film in which the conductive polymer is disposed on both surfaces of a porous base material via metal electrode layers, and a driving electrolyte solution. A manufacturing method of
A first step of immersing the composite membrane in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under normal temperature and normal pressure; and
A second step of removing the polar solvent from the composite membrane;
It is characterized by including.

  In an (electrolyte) driving electrolyte solution in a conventional polymer actuator element, a nonionic organic compound, particularly a nonionic polymer compound, has never been used as an electrolyte medium. This is because a nonionic organic compound is used as a medium (electrolyte medium), the affinity with the conductive polymer is low, the molecular chain of the polymer compound is entangled with the polymer, the medium This is because the movement of electrolytes such as ions is hindered by forming a high molecular weight. Furthermore, it has been difficult to fill the conductive polymer or the like with a nonpolar compound. However, in the present invention, by using the polymer actuator element containing the nonionic organic compound, by using the driving electrolyte as described above, an excellent stretch rate and response speed in an open system at normal temperature and pressure. It has been found that the polymer actuator element exhibits the following.

  More specifically, for example, a first step of immersing the conductive polymer or the composite film in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under normal temperature and pressure, and the conductive The polymer actuator element of the present invention can be manufactured by using a driving electrolyte filling method including a second step of removing the polar solvent from the conductive polymer or the composite film. In addition, when the said polar solvent is a solvent which is hard to volatilize over time under normal temperature normal pressure, it is not necessary to include the 2nd process of removing the said polar solvent.

  Although the polar solvent mixed with the nonionic organic compound is not particularly limited, a solvent that can be volatilized selectively by heat treatment or the like after filling is preferable. Even after the solvent such as water volatilizes, the nonionic organic compound remains as a solvent in the electrolyte and can function as an electrolyte medium. It is estimated that the amount of bending or the amount of displacement can be substantially equivalent.

  In the mixed solution, the polar solvent is preferably 3 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 20 to 35% by weight. In addition, since the viscosity of the nonpolar compound is one digit or more higher than that of water or acetonitrile, water, acetonitrile, or the like is particularly used for the purpose of shortening the permeation and swelling time of the polymer actuator element film (the composite film). The polar solvent is preferably a mixed solution of 10 to 50% by weight.

  Examples of the polar solvent used in the mixed solution include water, acetonitrile, lower alcohol, acetone, ethyl acetate, and methyl ethyl ketone. These may be used singly or in combination of two or more.

  In addition, the second step of removing the polar solvent from the conductive polymer or the composite film is not particularly limited as long as it is a treatment capable of selectively removing the polar solvent, and includes heat treatment, air drying treatment, and decompression treatment. Or a combination thereof.

  Since the method for producing a polymer actuator element of the present invention includes a process including the above-described method of filling the drive electrolyte, the drive electrolyte containing a nonionic organic compound, which has been difficult in the past, can be efficiently and simply filled. As a result, a polymer actuator element excellent in expansion / contraction rate and response speed can be easily produced.

(Driving condition)
The polymer actuator element driving method of the present invention includes a step of applying a voltage between the metal electrodes of any of the polymer actuator elements described above.

  In the driving method of the polymer actuator element of the present invention, the temperature of the driving electrolyte is not particularly limited, but is 10 to 100 ° C. in order to cause the conductive polymer to be electrostretched at a higher speed. It is preferable and it is more preferable that it is 20-60 degreeC.

Further, the concentration of the anion in the driving electrolyte is not particularly limited, but it is preferably 0.1 to 5.0 mol dm ⁻³ , and a large expansion / contraction ratio is obtained, so that the driving can be stably performed. Can do.

  Further, in the above driving method, it is more efficient to use as a bimorph type polymer actuator element provided with a composite film in which the conductive polymer is disposed on both surfaces of the porous substrate, respectively, via a metal electrode layer. This is preferable because the driving performance can be easily used.

  The voltage for driving the polymer actuator element is not particularly limited, but when the thickness is about 0.01 mm to 1 mm, the absolute value of the normal applied voltage (V) is 0.2. Although it can be -5V, it is preferable that it is 0.5-3V, and it is more preferable that it is 0.5-1.5V. By using the polymer actuator element of the present invention, even when the same driving performance as the conventional one is exhibited, it can be driven with the driving voltage set lower than the conventional one.

  Further, when the polymer actuator element of the present invention is used, for example, when a continuous displacement movement such as reciprocating left and right as a bimorph type is performed, the amplitude per one redox cycle of the polymer actuator element is It can be 50% or more of the length.

  Further, when the polymer actuator element is used, for example, when a continuous displacement movement such as reciprocating left and right as a bimorph type is performed, an opposite voltage is applied to each electrode at a cycle of 0.1 to 400 Hz. The period is preferably 0.2 to 300 Hz, and more preferably 0.5 to 200 Hz. In particular, by using the polymer actuator element of the present invention, it has become possible to drive the response to a large response frequency of 100 Hz or more, which has never been seen before. Furthermore, the polymer actuator element of the present application is capable of large displacement and deformation of 6% or more of the element length even at about 300 Hz.

(Use)
The polymer actuator element of the present invention can be suitably used for artificial muscles, robot arms, powered suits, artificial hands and artificial legs. In addition, the medical actuator element of the present invention is a medical device such as tweezers, scissors, forceps, snare, laser knife, spatula, clip, etc. in microsurgery technology, and various sensors or repair tools for performing inspections and repairs. , Hygrometers, hygrometer control devices, soft manipulators, underwater valves, industrial equipment such as soft transport devices, underwater mobiles such as goldfish, or hobby items such as moving fishing baits and propeller fins Can be suitably used.

  More specifically, the polymer actuator element is an OA device, an antenna, a device on which a person such as a bed or a chair is placed, a medical device, an engine, an optical device, a fixture, a side trimmer, a vehicle, a lifting device, a food processing device. , Cleaning device, measuring device, inspection device, control device, machine tool, processing machine, electronic device, electron microscope, electric shaver, electric toothbrush, manipulator, mast, game device, amusement device, riding simulation device, vehicle occupant presser Trucks consisting of drive parts or arc parts that generate linear drive force in valves, brakes, and lock devices used in general machines including equipment and aircraft accessory equipment extension devices, OA equipment, measuring equipment, etc. Drive unit that generates driving force to move the mold trajectory, or linear motion or curvilinear Work can be suitably used as a pressing portion for the. In addition to the above-described devices, devices, instruments, etc., the polymer actuator element is generally used in mechanical devices, such as a positioning device drive unit, a posture control device drive unit, a lifting device drive unit, and a transport device drive. Linear driving force is generated in the driving unit of the moving unit, the driving unit of the adjusting device such as the amount and direction, the driving unit of the adjusting device such as the shaft, the driving unit of the guiding device, and the pressing unit of the pressing device. It can be suitably used as a driving unit that generates a driving force for moving a track-type orbit including a driving unit or an arc portion, or a pressing unit that performs a linear operation or a curved operation. In addition, the polymer actuator element can be suitably used as a drive unit in a joint device, such as a joint unit that can be directly driven, such as a joint intermediate member, or a drive unit that gives a rotational motion to the joint.

  The polymer actuator element includes, for example, a drive unit of an inkjet part in an inkjet printer such as a CAD printer, a drive unit that displaces the optical axis direction of the light beam of the printer, and a head drive unit of a disk drive device such as an external storage device In addition, it can be suitably used as a drive unit for paper pressing contact force adjusting means in a paper feeding device of an image forming apparatus including a printer, a copier, and a fax machine.

  The polymer actuator element includes, for example, a measurement unit for moving a high frequency power supply unit such as a frequency sharing antenna for radio astronomy to the second focal point, a drive unit for a drive mechanism for moving the power supply unit, and mounting on a vehicle It can be suitably used for a drive unit of a lift mechanism in a mast such as a pneumatic operation telescopic mast (telescoping mast) or an antenna.

  The polymer actuator element is used in, for example, a massage unit drive unit of a chair-shaped massage machine, a nursing bed or medical bed drive unit, a drive unit of an attitude control device for an electric reclining chair, a massage machine, an easy chair, etc. Recliner backrest / Ottoman retractable rod drive part, chair backrest, legrest, etc. It can be suitably used for a drive unit used for turning driving of a bed of a care bed and the drive unit for posture control of a standing chair.

  The polymer actuator element includes, for example, a driving unit of a testing device, a driving unit of a pressure measuring device such as a blood pressure used in an extracorporeal blood treatment device, a driving unit of a catheter, an endoscope device, forceps, or the like, an ultrasonic wave A drive unit for a cataract surgery device using a chin, a drive unit for an exercise device such as a jaw movement device, a drive unit for a means for relatively expanding and contracting a member of a hoist for a sick person, It can be suitably used for a drive unit for posture control or the like.

  The polymer actuator element includes, for example, a drive unit for a vibration isolator that attenuates vibration transmitted from a vibration generating unit such as an engine to a vibration receiving unit such as a frame, and a valve operating device for an intake and exhaust valve of an internal combustion engine. It can be suitably used for a drive unit, a drive unit of an engine fuel control device, and a drive unit of an engine fuel supply device such as a diesel engine.

  The polymer actuator element includes, for example, a driving unit of a calibration device of an imaging apparatus with a camera shake correction function, a driving unit of a lens driving mechanism such as a home video camera lens, and a moving lens group of an optical device such as a still camera or a video camera. Drive unit for driving mechanism, drive unit for camera auto-focus unit, drive unit for lens barrel used in imaging devices such as cameras and video cameras, drive unit for auto-guider that captures light from optical telescope, stereoscopic camera and binoculars A lens driving mechanism or a lens barrel driving unit of an optical device having two optical systems such as a driving unit for applying a compressive force to a wavelength conversion fiber of a fiber type tunable filter used for optical communication, optical information processing, optical measurement, etc. Or it can use suitably for a press part, the drive part of an optical axis alignment apparatus, and the drive part of the shutter mechanism of a camera.

  The polymer actuator element can be suitably used for, for example, a pressing portion of a fixture such as a caulking fixing of a hose fitting to a hose body.

  The polymer actuator element includes, for example, a drive unit such as a winding spring of an automobile suspension, a drive unit of a fuel filler lid opener that unlocks a fuel filler lid of a vehicle, a drive unit of a bulldozer blade extension and retraction drive, an automobile It can be used suitably for the drive part of the drive device for automatically changing the gear ratio of the transmission for use or for automatically connecting and disconnecting the clutch.

  The polymer actuator element includes, for example, a drive unit of a lift device for a wheelchair with a seat plate lift device, a drive unit of a lift device for eliminating a step, a drive unit of a lift transfer device, a medical bed, an electric bed, an electric table, and an electric chair. , Nursing bed, lifting table, CT scanner, truck cabin tilting device, lifter, etc., as well as the driving unit for lifting and lifting of various lifting machinery, and the driving unit for loading and unloading device for special vehicles Can do.

  The polymer actuator element can be suitably used for, for example, a drive unit of a discharge amount adjusting mechanism such as a food discharge nozzle device of a food processing apparatus.

  The polymer actuator element can be suitably used, for example, for a drive unit such as a carriage or a cleaning unit of a cleaning device.

  The polymer actuator element includes, for example, a driving unit of a measuring unit of a three-dimensional measuring device that measures the shape of a surface, a driving unit of a stage device, a driving unit of a sensor part such as a detection system for a tire operating characteristic, Drive unit of the device that gives the initial speed of the impact response evaluation device, the drive unit of the piston drive device of the piston cylinder of the device including the in-hole water permeability test device, the drive unit for moving in the elevation angle direction in the concentrating tracking power generator, gas When the alignment is necessary in the driving device of the tuning mirror vibration device of the sapphire laser oscillation wavelength switching mechanism of the measuring device including the concentration measuring device of the above, the inspection device of the printed circuit board, and the flat panel display such as liquid crystal and PDP Drive unit of XYθ table, electron beam (E beam) system or focused ion beam ( IB) Adjustable aperture device driving unit used in charged particle beam systems such as systems, driving device for supporting device or detecting unit to be measured in flatness measuring device, and assembly of fine devices, semiconductor exposure apparatus It can be suitably used for a driving unit of a precision positioning device such as a semiconductor inspection device or a three-dimensional shape measuring device.

  The polymer actuator element can be suitably used for, for example, an electric razor drive unit and an electric toothbrush drive unit.

  The polymer actuator element has, for example, an imaging device for a three-dimensional object or a drive unit for a focus depth adjustment device for a CD and DVD readout optical system, and a shape to be driven with an active curved surface by a plurality of polymer actuator elements. A disk capable of linearly moving a moving unit having at least one of a magnetic head such as a variable mirror driving unit and an optical pickup that can easily change the focal position by forming a desired curved surface approximately by deforming Drive unit of device, drive unit of magnetic tape head polymer actuator element assembly head drive mechanism of linear tape storage system, etc., drive unit of image forming apparatus applied to electrophotographic copying machine, printer, facsimile, etc., magnetic The drive part of the mounting member such as the head member, the focusing lens group is the optical axis Drive unit for optical disk master exposure apparatus that controls driving in the direction, drive unit for head drive means for driving the optical head, drive unit for information recording / reproducing apparatus for recording information on the recording medium or reproducing information recorded on the recording medium In addition, it can be suitably used for a drive unit for opening / closing operation of a circuit breaker (distribution circuit breaker).

  The polymer actuator element includes, for example, a drive unit of a rubber composition press molding vulcanizing device, a driving unit of a component aligning device that aligns a transferred component into a single row / single layer and a predetermined posture, compression Drive unit of molding device, drive unit of holding mechanism of welding device, drive unit of bag making filling and packaging machine, drive unit of machine tool such as machining center, molding machine such as injection molding machine and press machine, printing device, coating device Drive unit for fluid application devices such as sprayers and lacquer spraying devices, drive unit for manufacturing devices that manufacture camshafts, etc., drive unit for lifting devices for lining materials, drive devices such as tuft-regulators for unwoven looms, tufting Drive unit for machine needle drive system, looper drive system, knife drive system, etc., drive unit for polishing machine that polishes parts such as cam grinder and ultra-precision machined parts, braking of ridge frame in loom Assembling of the drive unit of the device, the drive unit of the opening device that forms the opening of the warp yarn for inserting the weft in the loom, the drive unit of the protective sheet peeling device such as a semiconductor substrate, the drive unit of the threading device, and the electron gun for CRT Drive unit of shifter fork drive selection linear controller in torsion race machine for manufacturing torsion races with application to device drive, clothing trim, table cloth, seat cover, etc., horizontal movement mechanism of annealing window drive Driving unit, driving unit of glass melting furnace forherth support arm, driving unit for moving back and forth of rack of exposure apparatus such as phosphor screen forming method of color picture tube, driving unit of torch arm of ball bonding apparatus, XY of bonding head Component mounting process and measurement inspection in driving direction, chip component mounting and measurement using probes, etc. Drive unit for the process, elevating drive unit for the cleaning tool support of the substrate cleaning apparatus, drive unit for moving the detection head that scans the glass substrate, drive unit for the positioning device of the exposure apparatus that transfers the pattern onto the substrate, precision processing When manufacturing circuit devices such as conductive circuit elements and liquid crystal display elements such as conductor circuit elements and liquid crystal display elements in the sub-micron order in the fields such as micro-positioning device drive units, chemical mechanical polishing tool measurement device drive units. A drive unit for positioning a stage device suitable for an exposure apparatus and a scanning exposure apparatus used in the above, a drive unit for means for conveying or positioning a workpiece, etc., and a drive unit for positioning and conveying a reticle stage, a wafer stage, etc. , Precision positioning stage drive in the chamber, chemical mechanical polishing system As a drive unit for positioning devices for semiconductors or semiconductor wafers, a drive unit for semiconductor stepper devices, a drive unit for devices that accurately position in the processing machine introduction station, a machine tool such as an NC machine or a machining center, or a stepper in the IC industry The reference grating plate of the light beam scanning device is used in a drive unit of a passive vibration isolation device for various types of representative devices and an active vibration isolation device, an exposure device used in a lithography process for manufacturing semiconductor elements and liquid crystal display elements, and the like. It can be suitably used for a drive unit that moves in the direction of the optical axis of the light beam and a drive unit of a transfer device that transfers the light beam into the article processing unit in the direction transverse to the conveyor.

  The polymer actuator element can be suitably used for, for example, a driving unit for a probe positioning device of a scanning probe microscope such as an electron microscope and a driving unit for positioning a sample micro-motion device for an electron microscope.

  The polymer actuator element is, for example, a joint drive unit represented by a wrist of a robot arm in a robot or manipulator including an automatic welding robot, an industrial robot or a nursing robot, or a joint drive unit other than a direct drive type. , A robot finger itself, a drive unit of a motion conversion mechanism of a slide open / close type chuck device used as a robot hand, a micro object to be manipulated in an arbitrary state in a cell micro operation or a micro part assembly operation, etc. It is preferably used for a driving part of a micromanipulator for driving, a driving part of a prosthesis such as an electric prosthesis having a plurality of fingers that can be opened and closed, a driving part of a handling robot, a driving part of a prosthesis, and a driving part of a power suit it can.

  The polymer actuator element can be suitably used for, for example, a pressing portion of a device that presses an upper rotary blade or a lower rotary blade of a side trimmer.

  The polymer actuator element is suitably used for, for example, a driving unit for an accessory in a game machine such as a pachinko machine, a driving unit for an amusement device such as a doll or a pet robot, and a driving unit for a simulation apparatus for a boarding simulation apparatus. be able to.

  The polymer actuator element can be used, for example, in a valve drive unit used in all machines including the above devices, for example, a valve drive unit of an evaporative helium gas reliquefaction device, and a bellows pressure-sensitive control. Valve drive unit, drive unit for opening device that drives the frame, drive unit for vacuum gate valve, drive unit for solenoid-operated control valve for hydraulic system, and drive for valve incorporating motion transmission device using pivot lever It can be suitably used for the drive part of the valve of the movable nozzle of the rocket, the drive part of the suck back valve, and the drive part of the pressure regulating valve part.

  The polymer actuator element can be used, for example, as a pressing portion of a brake used in all machines including the equipment and the like. For example, the polymer actuator element is suitable for an emergency brake, a safety brake, a stop brake, and an elevator brake. It can be suitably used for a pressing portion of a braking device and a pressing portion of a brake structure or a brake system.

  The polymer actuator element can be used, for example, as a pressing portion of a locking device used in general machines including the above devices, etc., for example, a pressing portion of a mechanical locking device, a pressing portion of a vehicle steering lock device, and It can be suitably used for a pressing portion of a power transmission device having both a load limiting mechanism and a coupling release mechanism.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below. In addition, the evaluation item in an Example etc. measured as follows.

<Measurement of stretch rate>
The expansion / contraction rate (%) per oxidation-reduction cycle of the polymer actuator element produced by the following method was measured.

Each polymer actuator element has a strip shape with a length of 15 mm and a width of 2 mm, the polymer actuator element as an operating electrode, a platinum plate as a counter electrode, a lead connected to the end of each electrode, and each electrode as the above electrolyte solution While being held in, it is connected to a power source via a lead, and a potential (−0.7 to +0.7 V vs. Ag / Ag ⁺ ) at each frequency (Hz) is applied for one cycle to apply a displacement amount ( Displaced length) was measured. The expansion / contraction rate per oxidation-reduction cycle is obtained by dividing the displacement obtained by extending and contracting the working electrode by applying one cycle (one redox cycle) by the original length of the working electrode. (%) Was calculated.

<Measurement of displacement angle>
The displacement angle (°) of the polymer actuator element produced by the following method was measured.

  About each produced polymer actuator element, it sandwiched in the thickness direction of the polymer actuator element with a platinum terminal so that each of a pair of metal electrodes can be energized at a position 2 mm inside from one end, and the film surface is It was held so as to be parallel to the direction of gravity.

  Next, using a potentiostat (Bottensio Galvanostat HA-151, manufactured by Hokuto Denko Co., Ltd.) and a multifunction generator (manufactured by NF Circuit Design Block Co., Ltd., Wave Factory WF 1946), one of the pair of metal electrodes is the positive electrode and the other is the positive electrode A sine wave voltage of ± 0.5 V was applied so as to be a negative electrode, and then a voltage was applied so that an opposite voltage was applied to each metal electrode in a cycle of 0.5 Hz, and a displacement motion reciprocating left and right was performed. .

  The angle between the tangential direction of the displacement convex surface at the tip of the polymer actuator element in the reciprocating displacement movement and the state of gravity and the direction of gravity are measured at room temperature for both the right side displacement and the left side displacement, and this is averaged. The displacement angle was used.

<Measurement of response frequency>
The response frequency (Hz) of the polymer actuator element produced by the following method was measured.

  The behavior at a position 3 mm from the portion held by the clip was observed with a laser displacement meter (manufactured by Keyence Corporation, LC-4000) and measured. The visual evaluation was performed by fixing a bimorph element (width: 2 mm, measurement length: 15 mm) cut into a strip shape in a glass cell so as not to be affected by disturbance.

[Example 1]
As a porous base material, PTFE (polytetrafluoroethylene) filter film (pore diameter 15 μm, manufactured by Freon Industries), hydrophilic PTFE membrane filter (thickness 29 μm, porosity 60%, manufactured by Japan Gore-Tex), hydrophilic PTFE membrane filter (thickness 35 μm, porosity 83%, manufactured by Advantech Toyo Co., Ltd.) and paper non-woven separator (TF-40, manufactured by Nippon Kogyo Paper Co., Ltd.) were used. For Example 2 and later, a hydrophilic PTFE membrane filter (thickness 35 μm, porosity 83%, manufactured by Advantech Toyo Co., Ltd.) was used.

As shown in FIG. 1, first, an Au layer 12 of about 0.1 μm was constructed on both surfaces of a porous base material (base material layer 10) by sputtering. Using this as a working electrode, by electropolymerization method (conditions: pyrrole, 0.1 mol / l, 0 ° C.) in a methyl benzoate solution of TBACF ₃ SO ₃ at a current density of 0.2 mA cm ⁻² for 4 hours. Constant current electropolymerization was performed. Washed with electrolytic polymerization after acetone and dried in a room, a porous substrate and _PPy-CF ³ _SO 3 - 14 is ^{_{complexed, [PPy-CF 3 SO 3}} - -Au- porous substrate -Au- A PPy bimorph element having a five-layer structure of PPy—CF ₃ SO ₃ ⁻ ] was obtained. At this time, the composite PPy—CF ₃ SO ₃ ^— layer had a thickness of 10 to 15 μm. The bimorph element used in the air drive, _{PPy-CF 3} SO 3 by adjusting the electrolytic polymerization time ^- layer 14 was used to prepare a of about 5 [mu] m.

  As shown in Table 1, operation characteristics in a solution and in air were examined in a bimorph type actuator. A solution of acetonitrile (containing 1M LiTFSI (a lithium salt of ditrifluoromethanesulfonylimide)) solution was used as an electrolytic solution for electrolytic expansion and contraction. Evaluation in the air was performed by driving in a glycerol carbonate (containing 1 M LiTFSI (lithium salt of ditrifluoromethanesulfonylimide)) solution, and then lifting the electrolyte solution to wipe the surface electrolyte solution.

One using a hydrophilic PTFE membrane filter to a ^{_{substrate, PPy-CF 3 SO 3 -}} , PPy-TFSI - In both complexed with actuators, peeling from the substrate of the PPy layer 30,000 times It did not occur after driving, and showed stable deformation both in the electrolyte and in the air. On the other hand, those using a paper nonwoven fabric separator were operable both in the electrolyte solution and in the air, but when the operation was repeated, the nonwoven fabric of the base material was torn.

Further, FIG. 2 shows a cross-sectional photograph of the obtained PPy—CF ₃ SO ₃ ^— bimorph element. PPy—CF ₃ SO ₃ ^— electropolymerized using the Au layer formed on the surface of the hydrophilic PTFE membrane filter as a working electrode is polymerized so as to cover the surface of the hydrophilic PTFE membrane filter which is a porous body. PTFE-MF and PPy-CF ₃ SO ₃ ^- are firmly integrated, and stable driving is obtained without causing peeling over a long period of time. An SEM photograph of the surface of the bimorph element is shown in FIG. 3, and the surface of the obtained PPy—CF ₃ SO ₃ ^— had a shape with some unevenness. The thickness of the composite PPy—CF ₃ SO ₃ ^— is difficult to measure accurately because a layer composited with a hydrophilic PTFE membrane filter is formed, but the thickness of the obtained bimorph element can be measured with a micrometer. It was about 10-15 micrometers when it measured and calculated excluding the thickness of the hydrophilic PTFE membrane filter. In FIG. 2, (a) PPy—CF ₃ SO ₃ ^— layer, (b) Au layer, and (c) PTFE are shown.

[Example 2]
Figure 4 in the air-driven _{PPy-CF 3} SO 3 ^- shows the amplitude behavior with respect to the frequency of the bimorph actuator. Glycerol carbonate, which is a high boiling point organic solvent, is used for the driving electrolyte. When a voltage of 1.5 V was applied at a frequency of 0.5 Hz, an amplitude of 1.95 mm width was shown. As the frequency is increased, the amplitude width decreases. This actuator showed an amplitude behavior of 0.67 mm at 10 Hz and 0.12 mm at 100 Hz. In the vicinity of 200 Hz, the amplitude width was slightly improved, and an amplitude behavior of 0.25 mm was shown. This bimorph actuator also showed a response to a frequency of 300 Hz or higher, and showed a frequency response that greatly improved the performance of the conventional conductive polymer actuator (applied voltage: ± 1.5 V, measurement position: 4 mm from the fixed part). Position of).

  Furthermore, since glycerol carbonate, which is a high-boiling organic solvent, is used as the operating electrolyte, the electrolyte impregnated in the bimorph element is difficult to evaporate, and it has become possible to use it in the air for a long period of time. The bimorph element stored for about one month at room temperature after the treatment impregnated with the electrolytic solution maintained substantially the same performance as the frequency response measured immediately after the treatment.

Example 3
A polyethylene glycol (made by Wako Pure Chemical Industries) with a molecular weight of 200 is put into a beaker, and a predetermined amount is adjusted so that the concentration is 1 M, 100 mM, 10 mM, 1 mM while the lithium salt of ditrifluoromethanesulfonylimide (LiTFSI) remains as a solid powder. In addition, the solution was stirred at room temperature, and the solution of each concentration was used as the electrolyte.

The implementation in the electrolytic solution Example 2 in the same manner as PPy-CF ₃ SO ₃ ^- wiped electrolyte surface by pulling from the drive after the electrolyte in each solution a bimorph element was immersed for 2 days at room temperature.

  Next, each actuator was driven at a rectangular wave of 0.5 Hz under an applied voltage of 1.5 V, and its amplitude was measured with the same prescription as in Example 2. As the electrolyte concentration decreased, the actuator The amplitude decreased to 1.8 mm, 1.5 mm, 0.5 mm, and 0.1 mm. When the same drive and amplitude evaluation were performed after leaving for one week at room temperature and free of humidity, the amplitudes of the four actuators matched with a deviation within a range of ± 10%.

Example 4
Polyethylene glycol monolaurate and glycerol carbonate were mixed at a volume ratio of 1/1 and then dissolved in an equal volume of acetonitrile solution (including 1M LiTFSI), and PPy as in Example 2. -CF ₃ SO ₃ ^- was obtained actuator wiped electrolyte surface by pulling after driving in solution in the electrolyte solution after immersion for 5 hours at the bimorph element 40 ° C..

  When this actuator was cut to a size (2 mm width × 10 mm length) that resonates at about 20 Hz at room temperature and sine wave drive of 1.5 V was performed, even if the voltage application time passed 24 hours, Amplitude attenuation stopped within 5%.

Example 5
1/1 volume of polyethylene glycol having a molecular weight of 200 and a sulfoimide salt (N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide) as an ionic fluid (ionic liquid) the ratio mixture was dissolved in acetonitrile solution of an equal amount, example 2 in the same manner as PPy-CF ₃ sO ₃ ^- of the surface by pulling from the drive after the electrolytic solution in the solution after immersion for 5 hours at the bimorph element 40 ° C. The electrolytic solution was wiped off to obtain an actuator.

  This actuator is cut to a size that resonates at about 20 Hz (2 mm width × 10 mm length), and then placed in a thermostatic bath. The inside of the bath is maintained at −10 ° C. under humidity-free conditions, and a sine of 1.5 V When the wave drive was performed, the amplitude amount was kept at about 30% at room temperature (25 ° C.), and it was proved that it was put to practical use at a very low temperature.

Sectional drawing which shows typically the example of embodiment of the polymer actuator element of this invention Cross-sectional SEM photograph (650 times) of a bimorph actuator in which PPy-CF ₃ SO ₃ ^- and PTFE-MF are combined in an example of the present invention Surface SEM photograph (650 times) of a bimorph actuator in which PPy-CF ₃ SO ₃ ^- and a hydrophilic PTFE membrane filter are combined in an example of the present invention The graph which shows the frequency response of the air drive type actuator in the Example of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base material layer 12 Metal electrode layer 14 Conductive polymer

Claims (15)

A polymer actuator element comprising a conductive polymer and a driving electrolyte,
A polymer actuator element, wherein the driving electrolyte is a solution containing a nonionic organic compound that is liquid at normal temperature and pressure.   The polymer actuator element of Claim 1 provided with the composite film by which the said conductive polymer is arrange | positioned through the metal electrode layer on both surfaces of the porous base material, respectively.   The polymer actuator element according to claim 1, wherein the porous substrate is porous polytetrafluoroethylene.   The polymer actuator element according to claim 1, wherein the nonionic organic compound is an organic compound having a boiling point or a decomposition temperature of 180 ° C. or higher.   The polymer actuator element according to claim 1, wherein the nonionic organic compound is a polyether compound.   The polymer actuator element according to claim 1, further comprising an ionic liquid in the driving electrolyte. The ionic liquid is
A cation selected from at least one selected from the group consisting of tetraalkylammonium ion, dialkylimidazolium ion, trialkylimidazolium ion, pyrazolium ion, pyrrolium ion, pyrrolium ion, pyrrolidinium ion, and piperidinium ion;
7. A salt comprising a combination of PF ₆ ⁻ , BF ₄ ⁻ , AlCl ₄ ⁻ , ClO ₄ ⁻ , and an anion selected from the group consisting of sulfonium imide anions represented by the following formula (I): The polymer actuator element as described.
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (I)
[In the above formula (1), m and n are arbitrary integers. ]   The actuator element according to claim 1, wherein the conductive polymer includes pyrrole and / or a pyrrole derivative in a molecular chain. The polymer actuator element according to claim 1, wherein the conductive polymer is a film-like conductive polymer doped with perfluoroalkylsulfonylimide ions represented by the following formula (1).
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ] The polymer actuator element according to any one of claims 1 to 8, wherein the conductive polymer is a film-like conductive polymer doped with perfluoroalkylsulfonylmethide ions represented by the following formula (2). .
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ]   The polymer actuator element according to any one of claims 1 to 10, wherein the conductive polymer has an expansion / contraction ratio per oxidation-reduction cycle of 5% or more.   The polymer actuator element according to claim 1, wherein a response frequency of the polymer actuator element is 100 Hz or more. A method for producing a polymer actuator element comprising a conductive polymer and a driving electrolyte, wherein the driving electrolyte is a solution containing a nonionic organic compound that is liquid at normal temperature and pressure,
A first step of immersing the conductive polymer in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under a normal temperature and a normal pressure; and
A second step of removing the polar solvent from the conductive polymer;
A method for producing a polymer actuator element, comprising: A method for producing a polymer actuator element comprising a composite membrane in which the conductive polymer is disposed on both sides of a porous substrate via a metal electrode layer and a driving electrolyte,
A first step of immersing the composite membrane in a mixed solution containing a liquid nonionic organic compound, a polar solvent, and an electrolyte under normal temperature and normal pressure; and
A second step of removing the polar solvent from the composite membrane;
A method for producing a polymer actuator element, comprising:   A method for driving a polymer actuator element, comprising a step of applying a voltage between metal electrodes of the polymer actuator element according to claim 1.

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